The present invention relates to an azole derivative having a plant diseases controlling activity and plant growth regulating activity, a process for producing the azole derivative and an agricultural and horticultural composition containing the azole derivative as an active ingredient. More in detail, the present invention relates to
1) an azole derivative represented by the formula (I): ##STR2## wherein R.sup.1 and R.sup.2 respectively represent a (C.sub.1 -C.sub.5) alkyl group or a hydrogen atom; X represents a halogen atom, a (C.sub.1 -C.sub.5) alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or a CH, provided that R.sup.1 is not a hydrogen atom when R.sup.2 is a hydrogen atom, PA1 2) a process for producing the azole derivative represented by the formula (I), which process comprises the steps of PA1 3) an agricultural and horticultural composition having a fungicidal activity and a plant growth regulating activity, which comprises an effective amount of the azole derivative represented by the formula (I). PA1 (1) Compounds of triazoles or imidazoles represented by the following formula: ##STR9## wherein R.sup.1 represents a --CH.dbd.CH--X, a --C.tbd.C--X or a --CH.sub.2 --CH.sub.2 --X [wherein X is a hydrogen atom, an alkyl group, a hydroxyalky] group, an alkoxyalkyl group, a cycloalkyl group, a substituted aryl group which may be substituted, an aralkyl group which may be substituted, an aryloxyalkyl group which may be substituted or a heterocyclic group which may be substituted); R.sup.2 represents an alkyl group, a cycloalkyl group or an aryl group which may be substituted; Z represents a chlorine atom, a cyano group or a --OR.sup.3 (wherein R.sup.3 is a hydrogen atom, an acetyl group, an alkyl group, an alkenyl group or an aralkyl group) and Y represents a nitrogen atom or a CH, an acid addition salt thereof and a metal complex thereof [refer to Japanese Patent Application Laid-Open (KOKAI) No. 57-114577 (1982) corresponding to U.S. Pat. No. 4,507,140 and European Patent No. 52424.]. PA1 (2) Compounds of triazoles or imidazoles represented by the following formula: ##STR10## wherein R represents a cross-linking group: --(CH.sub.2).sub.n --(wherein n is 0, 1 or 2 ), a cross-linking group: a --CH.dbd.CH--, an --O--, an --S--, an --NH-- or a --C(.dbd.O)--; X represents a nitrogen atom or a CH; Y and Z may be the same or different from each other and respectively represents a halogen atom, an alkyl group, an alkoxy group, a haloalkoxy group, a haloalkyl group, a nitro group, a phenyl group or a phenoxy group, and m and p respectively represent 0, 1, 2 or 3, an acid thereof, a metal complex thereof and functional derivatives thereof [refer to Japanese Patent Application Laid Open No. 57-126479 (1982) corresponding to European Patent No. 52425]. PA1 (3) Derivatives of 1-hydroxyethylazole, represented by the following formula: ##STR11## wherein R represents an alkyl group, a cycloalkyl group which may be substituted or a phenyl group which may be substituted, X represents a nitrogen atom or a CH; Y represents a --OCH.sub.2 --, a --CH.sub.2 --CH.sub.2 -- or a --CH.dbd.CH--; Z represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, a halogenoalkyl group., a halogenoalkoxy group, a halogenoalkylthio group, phenyl group which may be substituted, a phenoxy group which may be substituted or phenylalkyl group which may be substituted or a phenylalkoxy group which may be substituted and m represents 0, 1, 2 or 3, an acid addition salt thereof and a metal complex thereof [refer to Japanese Patent Application Laid-Open (KOKAI) No. 57-16868 (1982) corresponding to U.S. Pat. No. 4,532,341 and European Patent No. 40345]. PA1 (4) Cycloaliphatic alcoholic compounds represented by the following formula: ##STR12## wherein R.sup.6 represents an unsubstituted phenyl group or a phenyl group substituted by from 1 to 5 groups selected from the group consisting of halogen atom(s), amino group(s), nitro group(s), cyano group(s), phenyl group(s), halogenophenyl group(s), (C.sub.1 -C.sub.10) alkyl group(s), halogeno (C.sub.1 -C.sub.10) alkyl group(s), (C.sub.1 -C.sub.10) alkoxy group(s), halogeno (C.sub.1 13 C.sub.10) alkoxy group(s), (C.sub.1 -C.sub.10) alkylthio group(s), (C.sub.1 -C.sub.10) alkylenedioxy group(s), (C.sub.1 -C.sub.10) alkylamino group(s) and di(C.sub.1 -C.sub.10) alkylamino groups; X represents a nitrogen atom or a methine group; a ring A is a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, an indane ring, a tetrahydronaphthalene ring or a benzocyclopeptane ring, each of the respective rings not having been substituted or having been substituted in the benzene ring thereof by from one to four of the above-mentioned substituents [refer to Japanese Patent Application Laid-Open (KOKAI) No. 58-189171 (1983) corresponding to U.S. Pat. No. 4,503,062 and European Patent No. 94146]. PA1 (5) Triazole compounds or imidazole compounds represented by the following formula: ##STR13## wherein W is a CH or a nitrogen atom; Q is a substituted or unsubstituted aryl group, particularly a substituted or unsubstituted phenyl group, a substituted or unsubstituted aralkyl, or a substituted or unsubstituted alkyl group; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 may be the same or different from each other and respectively represent a hydrogen atom, a hydroxy group, an alkyl group, a cycloalkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, or any of the pairs of R.sup.1 and R.sup.2, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6 or R.sup.7 and R.sup.8 represents a carbonyl group (C.dbd.O) together with the adjacent ring-carbon atom; R.sup.9 and R.sup.10 may be the same or different from each other and represent respectively a hydrogen atom, an alkyl group, a cycloalkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted phenyl group and n is 0 or 1, a stereoisomer thereof, an acid addition salt thereof and a metal complex thereof [refer to Japanese Patent Application Laid-Open (KOKAI) No. 60-215674 (1985) corresponding to European Patent No. 153797]. PA1 a) (i) reacting an alkyl ester of 2-oxocyclopentanecarboxylic acid with a substituted benzyl halide and reacting the thus obtained alkyl ester of 1-(substituted benzyl)-2-oxocyclopentanecarboxylic acid with a (C.sub.1 -C.sub.5) alkyl halide, (ii) reacting an alkyl ester of 3-(C.sub.1 -C.sub.5 alkyl)-2-oxocyclopentanecarboxylic acid with a substituted benzyl halide or (iii) reacting 1-(substituted benzyl)-3-(C.sub.1 -C.sub.5 alkyl)-2-oxocyclopentanecarboxylic acid with a (C.sub.1 -C.sub.5) alkyl halide, thereby obtaining an ester derivative of cyclopentanecarboxylic acid represented by the formula (V): ##STR18## wherein R.sup.1 and R.sup.2 respectively represent a (C.sub.1 -C.sub.5) alkyl group or a hydrogen atom; R represents a (C.sub.1 -C.sub.5) alkyl group; X represents a halogen atom, a (C.sub.1 -C.sub.5) alkyl group or a phenyl group and n represents an integer of from 0 to 2, provided that R.sup.1 is not a hydrogen atom when R.sup.2 is a hydrogen atom, PA1 b) subjecting the thus obtained ester derivative of cyclopentanecarboxylic acid to hydrolyric decarboxylation, thereby obtaining a cyclopentanone derivative represented by the formula (IV): ##STR19## wherein R.sup.1, R.sup.2, X and n respectively represent the same defined as above, PA1 c) subjecting the thus obtained cyclopentanone derivative to an oxirane reaction while using sulfonium ylide or oxosulfonium ylide, or subjecting a methylenecyclopentane derivative obtained from the thus obtained cyclopentanone derivative by Wittig reaction and represented by the formula (III): ##STR20## wherein R.sup.1, R.sup.2, X and n respectively represent the same defined as above, to epoxidation, thereby converting the cyclopentanone derivative into an oxirane derivative represented by the formula (II): ##STR21## wherein R.sup.1, R.sup.2, X and n respectively represent the same defined as above, and then PA1 d) reacting the thus obtained oxirane derivative with a 1,2,4-triazole or an imidazole represented by the formula (VI): ##STR22## wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a CH. PA1 i) Inhibition of vegetative grow of plants, particularly the growth inhibition of the height of plants, PA1 ii) Increasing activity of the content of the useful component of plants, and
a) (i) reacting an alkyl ester of 2-oxocyclopentanecarboxylic acid with a substituted benzyl halide and reacting the thus obtained alkyl ester of 1-(substituted benzyl)-2-oxocyclopentanecarboxylic acid with a (C.sub.1 -C.sub.5) alkyl halide, (ii) reacting an alkyl ester of 3-(C.sub.1 -C.sub.5 alkyl)-2-oxocyclopentanecarboxylic acid with a substituted benzyl halide, or (iii) reacting 1-(substituted benzyl)-3-(C.sub.1 -C.sub.5 alkyl)-2-oxocyclopentanecarboxylic acid with a (C.sub.1 -C.sub.5) alkyl halide, thereby obtaining an ester derivative of cyclopentanecarboxylic acid represented by the formula (V): ##STR3## wherein R.sup.1 and R.sup.2 respectively represent a (C.sub.1 -C.sub.5) alkyl group or a hydrogen atom; R represents a (C.sub.1 -C.sub.5) alkyl group; X represents a halogen atom, a( C.sub.1 -C.sub.5) alkyl group or a phenyl group and n represents an integer of from 0 to 2, provided that R.sup.1 is not a hydrogen atom when R.sup.2 is a hydrogen atom, PA2 b) subjecting the thus obtained ester derivative of cyclopentanecarboxylic acid to hydrolyric decarboxylation, thereby obtaining a cyclopentanone derivative represented by the formula (IV): ##STR4## wherein R.sup.1, R.sup.2, X and n respectively represent the same defined as above, PA2 c) subjecting the thus obtained cyclopentanone derivative to an oxirane reaction while using sulfonium ylide or oxosufonium ylide or subjecting a methylemecyclopentane derivative obtained from the thus obtained cyclopentanone derivative by Wittig reaction and represented by the formula (III): ##STR5## wherein R.sup.1, R.sup.2, X and n respectively represent the same defined as above, into epoxidation, thereby converting the cyclopentanone derivative into an oxirane derivative represented by the formula (II): ##STR6## wherein R.sup.1, R.sup.2, X and n respectively represent the same defined as above, and then PA2 d) reacting the thus obtained oxirane derivative with an 1,2,4-triazole or an imidazole represented by the formula (VI): ##STR7## wherein M represents a hydrogen atom or an alkali metal atom and A represents a nitrogen atom or a --CH.dbd., thereby obtaining the azole derivative represented by the formula (I): ##STR8## wherein R.sup.1 and R.sup.2 respectively represent a (C.sub.1 -C.sub.5) alkyl group or a hydrogen atom; X represents a halogen atom, a (C.sub.1 -C.sub.5) alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or a CH, provided that R.sup.1 is not a hydrogen atom when R.sup.2 is a hydrogen atom, and
The damage of the crops due to various plant diseases is enormous, and also, a problem due to the environmental pollution by the chemicals for controlling these plant diseases has arisen.
Accordingly, an offer of an agricultural and horticultural chemical which has a controlling effect against the plant diseases, is low in toxicity to men, beasts, birds and fishes and is low in phytotoxicity to useful plants, that is, an agricultural and horticultural chemical which is high in safety on handling, small in influence to the environment and has an excellent controlling effect against plant diseases in a broad range has been demanded.
In order to fulfill such a demand, the following agricultural and horticultural fungicides have hitherto been proposed.
As a result of the studies of some of the present inventors for providing an agricultural and horticultural fungicide which is high in safety on handling, is small in influence to the environment and shows an excellent controlling effect against the plant diseases of a broad range, they have found an azole derivative represented by the following formula: ##STR14## wherein X represent respectively a halogen atom, an alkyl group, a haloalkyl group, a phenyl group, a cyano group or a nitro group; n represents an integer of from 0 to 5 and A represents a nitrogen atom or a CH, provided that X may be the same or different from each other when n is 1 to 5 [refer to Japanese Patent Application Laid-Open (KOKAI) No. 62-149667 (1987) corresponding to U.S. patent application Ser. No. 06/903,992].
The present inventors have further studied a synthesis of many azole derivatives and an examination on the utility thereof in order to obtain an agricultural and horticultural fungicide which is low in toxicity to men and beasts, is high in safety on handling and shows an excellent controlling effect against plant diseases of a broad range, and as a result it has been found that an azole derivative represented by the formula (I): ##STR15## wherein R.sup.1 and R.sup.2 respectively represent a (C.sub.1 -C.sub.5) alkyl group or a hydrogen atom; X represents a halogen atom, a (C.sub.1 -C.sub.5) alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or a CH, provided that R.sup.1 is not a hydrogen atom when R.sup.2 is a hydrogen atom, not only has the afore-mentioned specific properties but also can be effectively applied as a plant growth regulating agent, and on the basis of their finding, the present invention have been attained.
Namely, the object of the present invention is to provide with an azole derivative having the utility as the active ingredient of the agricultural and horticultural composition having a plant diseases controlling activity and a plant growth regulating activity, a process for producing the azole derivative, and an agricultural and horticultural composition which contains, as an active ingredient, the azole derivative which shows an excellent controlling effect on the plant diseases in a broad range and at the same time, shows a plant growth regulating effect, is low in toxicity and is excellent in safety on handling.